Cobalt-platinum catalyst

ABSTRACT

THE INVENTION RELATES TO A COBALT-PLATINIUM CATALYST FOR EFFECTING THE ADDITION OF $SI-H COMPOUNDS TO UNDSTURATED ORGANIC COMPOUNDS AND ESTERIFICATION OF $SI-H COMPOUNDS WITH COMPOUNDS HAVING AN ACTIVE HYDROGEN IN THE PRESENCE OF PLATINUM CONTAINING CATALYSTS.

United States Patent 3,714,212 COBALT-PLATINUM CATALYST Guenther Fritz Lengnick, Adrian, Mich., assignor to Staulfer-Wacker Silicone Corporation, Adrian, Mich. No Drawing. Filed Dec. 30, 1971, Ser. No. 214,445 Int. Cl. C07f 7/08, 7/18 US. Cl. 260-4481 E 9 Claims ABSTRACT OF THE DISCLOSURE The invention relates to a cobalt-platinium catalyst for effecting the addition of ESlH compounds to unsaturated organic compounds and esterification of ESl-H compounds with compounds having an active hydrogen in the presence of platinum containing catalysts.

The present invention relates to a novel catalyst and particularly to a novel catalyst for effecting the addition of organosilicon compounds to unsaturated organic compounds, and esterification of the organosilicon compounds with compounds having an active hydrogen. More particularly the invention relates to a cobalt catalyst for effecting the addition of silicon bonded hydrogen compounds to aliphatic unsaturated organic compounds and esterification of silicon bonded hydrogen compounds with organic compounds having an active hydrogen.

Heretofore various platinum catalysts and complexes thereof have been used in the preparation of various organosilicon compounds, These platinum catalysts included compounds such as chloroplatinic acid, various platinum chloride-ethylene complexes, platinum chloride-cyclopropane catalysts and various complexes derived by reacting alcohols, ethers and aldehydes with a chloroplatinic acid.

It is therefore an object of this invention to provide a novel catalyst. Another object of this invention is to provide a novel cobalt-platinum catalyst. Another object of this invention is to catalyze the addition of ESlH containing compounds to unsaturated organic compounds in the presence of a cobalt-platinum catalyst at low temperatures. A further object of this invention is to catalyze the esterification of -=-SiH containing compounds to organic compounds having an active hydrogen.

The foregoing objects and others which will become apparent from the following description are accomplished in accordance with this invention, generally speaking, by reacting in the presence of a catalyst having the empirical formula (CO) (Co) Pt(Cl) a compound containing a silicon bonded hydrogen group (ESl-H) and a compound having carbon-to-carbon unsaturation.

or a compound having an active hydrogen.

Various methods may be used to prepare the platinum catalyst of this invention. For example, a platinum dichloride may be reacted with dicobalt octacarbonyl in the presence of a solvent at an elevated temperature and thereafter washed with a non-solvent, such as, ligroin to provide a compound which is identified as dichloro bis (tetracarbonyl cobalt)-platinum IV.

The cobalt-platinum catalyst of this invention is effective for the addition of an unlimited class of organosilicon compounds containing a silicon hydrogen bond to an unlimited class of organic compounds having carbon-carbon unsaturation or compounds having an active hydrogen group. Also this catalyst is eifective for the esterification of ESl-H compounds with compounds having an active hydrogen.

The organosilicon compounds which contain a siliconhydrogen bond may be monomeric or polymeric. How- "ice ever, the silicon-hydrogen containing reactant must containing at least one silicon bonded hydrogen atom per molecule and preferably no more than about two hydrogen atoms to any one silicon atom.

Suitable monomeric silicon compounds and organosilicon compounds containing silicon-hydrogen bonds which may be used in the practice of the present invention are those represented by the formula:

wherein R represents an organic radical, preferably a member selected from the class consisting of monovalent hydrocarbon radicals, halogenated monovalent hydrocarbon radicals and cyanoalkyl radicals; X is a member selected from the class consisting of hydrogen, OR radicals and OOCR radicals; a is a number of from 0 to 3; b is a number of from 1 to 2 and the sum of a and b is from 1 to 4. Where more than one R radical is present in the compound the various R radicals may be the same or different.

Among the radicals represented by R are alkyl radicals, e.g. methyl, ethyl, propyl, octyl, octadecyl and the like; cycloalkyl radicals such as cyclohexyl, cycloheptyl and the like; aryl radicals such as phenyl, naphthyl, tolyl, xylyl and the like; aralkyl radicals such as benzyl, phenylethyl and the like; haloaryl radicals and haloalkyl radicals such as chlorophenyl, chloromethyl, dibromophenyl and the like. In addition to the radicals mentioned above, R may also be an unsaturated aliphatic radical such as vinyl, allyl, cyclohexenyl and the like. In the preferred embodiment, R is methyl or a mixture of methyl and phenyl radicals.

Examples of suitable silicon compounds represented by the above formula which can be employed in the present invention are: methyldichlorosilane, phenyldichlorosilane, diethylchlorosilane, dimethylethoxysilane, diphenylchlorosilane, trimethoxysilane, triacetoxysilane, diacetoxyphenylsilane, dichlorosilane, dibromosilane, pentachlorodisiloxane,-and the like.

Suitable silicon hydrogen containing compounds useful in the practice of the present invention are those in which each molecule contains at least one silicon-hydrogen bond. Within this category are included oganopolysiloxanes and various polysilalkylene compounds containing, for example, a

grouping in which R is a divalent hydrocarbon radical having from 1 to 8 carbon atoms or a nitrogen atom, such as, the organosilazanes which are characterized by an S:iNS:ilinkage in the polymer.

Suitable examples of organopolysiloxanes are polymers and copolymers containing up to one or more of the units having the formulae:

R3Sl0o 5, O1 along with at least one unit per molecule having the formulae:

RHSiO, R HSiO HSiO H SiO, or RH SiO where R is as previously defined. Any of the silicon hydrogen compounds described above, are operative in the practice of the present invention; however, it is preferred that the silicon hydrogen compound be an organopolysiloxane such as an organocyclopolysiloxane:

(RHSiO) or an organopolysiloxaue polymer or copolymer having the formula:

( )y )z 4Yz where R is as previously defined: x is a number of at least 4; y is a number of from 0.5 to 2.49; z is a number of from 0.001 to l and the sum of y and z is equal to from 1 to 2.5.

Compounds containing carbon-to-carbon unsaturation, particularly unsaturated compounds containing olefinic or acetylenic unsaturation which can react with the compounds described above containing the silicon hydrogen linkage includes substantially all of the aliphatically unsaturated compounds known in the art. Thus, the aliphatically unsaturated compound can be monomeric or polymeric material. It may contain only carbon and hydrogen or it may also contain another element or elements. Where the aliphatically unsaturated compound contains an element other than carbon and hydrogen, preferably the other element is oxygen, halogen, nitrogen, silicon or mixtures of these elements. Aliphatically unsaturated compounds can contain a single pair of carbon atoms linked by multiple bonds. Among the many unsaturated hydrocarbons applicable to the present invention can be mentioned for purposes of illustration; ethylene, propylene, butylene, octylene, styrene, butadiene, pentadiene, 2-pentene, 2-divinylbenzene, vinyl acetylene and the like. Preferably the unsaturated compound is one containing no more than about 18 carbon atoms in the chain.

Included in the oxygen containing unsaturated compounds which may be employed in the practice of the invention are methylvinyl ether, divinyl ether, pentavinyl ether; the monoallyl ether of ethylene glycol, allyl aldehyde, methylvinyl ketone, phenylvinyl, ketone, acrylic acid, methacrylic acid, methacrylate, phenylmethacrylate, vinyl acetic acid, vinyl octoate, vinyl acetate, maleic acid, linoleic acid and the like. Other unsaturated compounds are acyclic and heterocyclic materials containing aliphatic unsaturation in the ring, such as, cyclohexene, cyclopentadiene, dihydrofuran, dihydropyrene and the like. The sulfur analogues of many of the unsaturated oxygen containing materials may also be employed in the practice of this invention. In addition to compounds containing carbon, hydrogen and oxygen, compounds containing other elements may also 'be used. Thus, halogenated derivatives of any of the materials described above can be employed including the acyl chlorides as well as compounds containing a halogen substituent on a carbon atom other than a carbonyl carbon atom. Thus, halogen containing materials include, for example, vinyl chloride, the vinyl chlorophenyl esters, the allyl esters, trichloroacetic acid and the like.

Other types of unsaturated materials which are useful in the practice of this invention include compounds containing nitrogen sbstituents such as acrylonitrile, allylcyanide, nitroethylene and the like. Unsaturated polymeric materials containing aliphatic unsaturation such as polyester resins prepared from polybasic saturated or unsaturated acids and polyhydric unsaturated alcohols may also be used in the practice of this invention.

Other unsaturated compounds which may be used in the practice of this invention are those compounds containing silicon such as the materials commonly referred to as organosilicon monomers or polymers. The scope of the organosilicon compounds which are applicable to the process is identical to the scope of the silicon hydrogen compound useful in the practice of this invention. For example, the unsaturated organosilicon compounds are identical to the silicon hydrogen, except that the silicon bonded hydrogen is replaced by silicon bonded organic radicals containing at least one pair of aliphatic carbon atoms linked with multiple bonds. Although it is preferred that the organosilicon compounds be free of silicon bonded hydrogen atoms, organosilicon compounds containing both silicon bonded hydrogens and silicon bonded unsaturated radicals may be used. The only requirement of these unsaturated silicon compounds is that there be at least one unsaturated organic radical attached 4 to the silicon atom per molecule. Thus, the unsaturated organosilicon compounds include silanes, polysilanes, siloxanes, silazanes as Well as monomeric or polymeric materials containing silicon atoms joined together by methylene or polymethylene groups or by phenylene groups.

Suitable organic compounds having an active hydrogen are alcohols, organic acids, polyethers or polyesters, diethylhydrogen phosphate, oximes and the like. Examples of alcohols are aliphatic alcohols having from 1 to 22 carbon atoms, methanol, butanol, octanol, dodecanol, cyclic aliphatic alcohols such as cyclohexanol, and aryl alcohols such as phenol.

Examples of suitable unsaturated silicon compounds which may be used are methylvinyldichlorosilane, vinyltrichlorosilane, allyltrichlorosilane, methylphenylvinylchlorosilane, phenylvinyldichlorosilane, diallyldichlorosilane, vinyl-betacyanoethyldichlorosilane, cyclic polysiloxanes such as cyclic trimer of methylvinylsiloxane, cyclic pentamer of methylvinylsiloxane, cyclic tetramer of methylvinylsiloxane, cyclic tetramer of vinylphenylsiloxane and the like.

The ratio of silicon hydrogen compound and unsaturated compound employed can vary within extremely wide limits. Generally, one silicon hydrogen bond is equivalent to one olefinic double bond or one-half acetylenic triple bond so that this equivalency establishes the general order of magnitude of the two reactants used. How ever, for many purposes it may be desirable to employ an excess of one of the reactants to facilitate the completion of the reaction or to insure that the reaction product contains either silicon hydrogen bonds in the unreacted state or contains one or more pairs of carbon atoms linked by multiple bonds. In general, however, the ratio of the reactants are selected so that there are present from about 0.5 to 20 silicon hydrogen linkages available for each unsaturated carbon-carbon double bond and from about 1.0 to 15 silicon hydrogen linkages for each carbon-carbon triple bond.

One of the advantages of the dichloro-bis(tetracarbonyl-cobalt)-platinum IV catalyst of this invention is that it will produce the desired reaction between the silicon hydrogen compound and the unsaturated compound in very small quantities. Thus, the catalyst may be used in concentrations as low as .001 percent and up to about 5 percent by weight or higher based on the total weight of the unsaturated compound and the silicon hydrogen compound. .Because of the economics a particularly low level of catalyst, that is from about 0.05 to about 2 percent by weight is used. An additional advantage of employing a low concentration of catalyst is that it insures a low quantity of catalyst residue in the reaction product. Consequently, it has been found that satisfactory rates of reaction are obtained at reaction temperatures where about 0.05 to 2 percent by weight of catalyst are present.

Due to the fact that the catalyst is a solid material and is employed in minute quantities, it is desirable to use the catalyst as a dilute solution to facilitate uniform dispersion of the catalyst in the reaction medium. Suitable diluents are any materials which are solvents for the catalyst and which are inert to the reactants under the reaction conditions. The preferred diluents are hydrocarbon solvents such as aromatic hydrocarbons, including benzene, toluene, xylene as well as aliphatic solvents such as aliphatic mineral spirits. In addition to these hydrocarbon solvents, the diluent may be an alcohol or an ether such as isopropanol, octanol or tetrahydrofuran. Generally the amount of diluent will range from 0.1 to 5 percent by weight based on the weight of the catalyst.

To effect the addition reactions with the dichloro-bis (tetracarbonyl-cobalt)-platinum .IV, the reactants and the diluted catalyst are thoroughly mixed and the reaction mixture heated to the desired temperature which is generally of the order of from 50 to C. and the reaction is allowed to go to completion. The time required 3. The method of claim 1 wherein the silicon com pound has the formula;

(mi umumnab in which R is an organic radical, X is selected from the group consisting of halogen, organoxy radicals and acyloxy radicals, a is a number of from to 3, b is a number'of from 1 to 2 and the sum of a and b is equal to from 1 to 4.

4. The method of claim 1 wherein the silicon'compound has the formula:

2 in which R is a monovalent organic radical, y is a number of from 0.5 to 2.49,z is a number of from 0.001 to 1.0 and the sum of y and z is equal to 1.0 to 2.5.

5. The method of claim 1 wherein the unsaturated organic compound has the formula:

( i .si 0

in which R is an organic radical, R is an organic radical containing aliphatic-carbon: atoms linked by multiple bonds, y. is a number of from 0.5 to 2.49, z is a number of from 0.001 to 1.0 and the sum of y and z is equal to 1.0 to 2.5.

6. The method of claim 5 wherein the silicon compound has the formula:

mu unnwug in which R is a monovalent organic radical, y is a number of from 0.5 to 2.49, z is a number of from 0.001 to 1.0 and the sum of y and z is equal to 1.0 to 2.5.

7. A method for preparing organosilicon compositions containing carbon-oxygen-silicon bonds which comprises in which R is an organic radical, a is a number of from 0 to 3. v a

9. The method of claim 7 wherein the silicon compound has the formula:

in which R is a monovalent organic radical, y is a number of from 0.5 to 2.49, z is a number of from .001 to 1.0 and the sum of y and z is equal to 1.0 to 2.5.

References Cited UNITED STATES PATENTS 3,159,662 12/ 1964 Ashby 260448.2 E 3,470,225 9/1969 KnOrre et a1. 260448.2 E 3,516,946 6/1970 Modic 260448.2 'E X 3,567,755 3/1971 Seyfried et al. 260448.2 E 3,631,086 12/1971 Seyfried et 260448.2 E

JAMES E. POER, Primary Examiner P. F. SHAVER, Assistant Examiner A us. c1. X.R.

23 2os c, 367; 260448.8 R 

